BRPI1009755B1 - “Process for enriching a homogeneous catalyst of a process flow and process for tridecanol production” - Google Patents

Description

(54) Title: PROCESS FOR THE ENRICHMENT OF A HOMOGENEOUS CATALYST OF A PROCESS FLOW AND PROCESS FOR THE PRODUCTION OF TRIDECANOL (51) Int.CI .: B01J 31/40; B01J 31/18 (30) Unionist Priority: 27/02/2009 DE 102009001225.7 (73) Holder (s): EVONIK DEGUSSA GMBH (72) Inventor (s): MARKUS PRISKE; GOTZ BAUMGARTEN; HANS-GERD LUKEN; ALFRED KAIZIK; KLAUS-DIETHER WIESE; UWE ERNST; PATRICK MUHLACK

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Descriptive Report of the Invention Patent for PROCESS FOR THE ENRICHMENT OF A HOMOGENEOUS CATALYST OF A PROCESS FLOW AND PROCESS FOR THE PRODUCTION OF TRIDECANOL.

The present invention relates to a process for the enrichment of a homogeneous catalyst in a process flow, which contains that homogeneous catalyst as a component. For enrichment, the process flow is conducted through at least one membrane.

Catalyst systems used in homogeneous catalysis must generally be removed entirely or partially from the respective reaction mixture. The reasons for this may be demands regarding the purity of the product or the recovery of the catalyst system as recyclable material, which, for example, can be returned directly or indirectly to the reaction.

Especially when transition metal complexes such as, for example, rhodium are used as catalysts or when expensive binders are used, the separation of the catalyst system represents an important process stage due to the costs of the catalyst. Technical processes, which are carried out with the use of homogeneous transition metal complexes are, for example, telomerizations, metatheses, hydrogenations or hydroformylations. Reactions with rhodium complexes are technically disclosed and associated with relatively high catalyst costs.

Rhodium complexes are used as a catalyst, for example, in the hydroformylation of olefins on a technical scale to aldehydes and / or alcohols richer in a carbon atom. In this case, rhodium complexes with phosphine, phosphite, phosphonite or phosphonite binders are used as a catalyst.

The type of separation can have an essential influence on the economics of the global process. The separation of the catalyst from the reaction mixture can be carried out in the simplest way exclusively by means of a thermal separation process, for example, in which the reaction product and possibly the starting product is separated from the reaction mixture containing catalyst by evaporation. The disadvantage in these

2/26 processes is that the catalyst and / or the binder can decompose during distillation. The by-products of the catalyst in the distillation residue often cannot be transformed into an active catalytic system in the process. For this reason, they must be unloaded and elaborately terminated before the process is renewed. This applies especially to the processing of hydroformylation mixtures, which contain rhodium complexes with binders as catalysts, which complex rhodium more weakly than phosphines. In distillation, these ligand complexes, due to the lack of stabilization, can decompose through carbon monoxide, which can lead to a rhodium cluster. Under hydroformylation conditions, rhodium clusters cannot be reacted to the active catalyst. In addition, partial distillation of binders may occur during distillation.

A potentially protective separation of homogeneous catalytic systems is offered by concentrating process flows containing homogeneous catalysts with membranes in an interconnection of one or more stages.

EP 0.781.166 describes the separation of dissolved rhodium-organophosphite complex catalyst, as well as the free binder from a hydroformylation reaction mixture on a membrane of at least 90% by mass, the catalyst and the free binder. The membrane polymer includes teflon, polydimethylsiloxane (PDMS), polyethylene, polyisobutadiene, polystyrene, polymethyl methacrylate, polyvinyl chloride, cellulose diacetate, polyvinylidene chloride and polyacrylonitrile. The separation of high boiling solvents from the catalytic system is not described.

EP 1,232,008 describes the separation of high boiling solvents from a return flow of the catalyst by means of a membrane (PDMS). The return flow is obtained in the distillation processing of a discharge of a catalyzed reaction in a metallorganic way. In this case, the starting products and the primary products are distilled and as a bottom product a high boiling mixture predominates, in which the catalytic system is dissolved. This is returned to the reactor. Since

3/26 small amounts of high-boiling solvents are formed in the process, some of which must be separated to maintain a constant high-boiling solvent concentration. In EP 1,232,008, the separation of the high boiling solvents from the bottom product is carried out with the addition of a diluent. In this way, so much diluent is added that the proportion of high boiling solvents in the solution, which is added to the membrane, is less than 50% by weight. The separation of high boiling solvents occurs in the temperature range of 10 ° C to 50 ° C and in the pressure range of 0.1 MPa to 10 MPa. The addition of diluents is disadvantageous, as the amount of substance carried through the membrane increases. In addition, a part of the diluent added with the high boiling solvents is separated, resulting in costs for the diluent or for its recovery.

DE 10 2005 046250 describes a process for the separation of a metallorganic catalytic system. In this case, in a first stage, the organic reaction discharge is separated into a retentate with most of the catalytic system and a permeate, which consists of the starting products, primary products, high-boiling solvents and catalytic system. The retentate is directly returned to the reactor. The permeate is separated by distillation into a top product, which contains mainly starting products and primary reaction products and a bottom product with the catalytic system, dissolved in high boiling solvents. In this report, as an optional processing variant, it is explained that from the bottom product, before being returned to the reactor, a part of the high-boiling solvents is separated by means of a membrane. As usable membrane materials, in principle, mention is made of polydimethylsiloxane (PDMS), polyimide (Pl), polyamidimide (PAI), acrylonitrile / glycidyl methacrylate (PANGMA), polyamide (PA), polyether ketone (PEEK), polymers with intrinsic microporosity (PIM), as well as hydrophobic ceramic membranes. However, for the removal of high-boiling solvents with membranes, no particularities are mentioned, such as, for example, types of membranes

4/26 usable.

DE 10 2005 060784A1 describes a process for recovering a stream enriched in a metal complex catalyst (> 200 Dalton). The reactor discharge is separated by distillation into a low-boiling flow and a higher-boiling bottom flow, which contains the catalyst. The bottom stream is separated with a membrane into a permeate stream and a catalyst enriched retentate stream, which is wholly or partly returned to the reaction. Only ceramic membranes with a separation limit (MWCO) above 500 Dalton are indicated. There is no information on the activity as an essential grade for the quality of the retained catalytic system.

The exemplified catalyst has a molecular weight of about 12000 Dalton and, therefore, is in an order of magnitude above the catalysts technically used. A transmission to technically relevant catalytic systems and of lower molecular weight is not possible with the explanation of DE 10 2005 060784A1.

In addition, it is not indicated to which retention the separation limit refers and in which material system the separation limit has been determined. The data usually refer, according to the manufacturer, to a retention of 90 or 95%. The separation limit does not serve as an absolute limit, but as qualitative aid for choosing a membrane to a problem of concrete separation (see Melin, Rautenbach: Membranverfahren 2nd edition 2004 Springer-Verlag Berlin, Heidelberg.). Therefore, it is questionable whether the separation limits indicated above are valid for the metal complex catalyst. The need for ligand retention is not mentioned.

The listed membranes are exclusively porous membranes, whose separation limits, as shown below, are not suitable for the catalytic system according to the process. In the listed membranes, in addition to the various ceramic membranes, only polytetrafluoroethylene, polyvinylidene fluoride (PVDF), polysulfone, polyether sulfone, polydimethylsiloxane are mentioned as possible membrane materials

5/26 (PDMS), polyether ketone, polyamide and polyimide.

US 2006 / 0246273A1 describes a modern polymer with intrinsic microporosity (PIM). Based on the rigid spiro bond, this polymer or the polymeric mixtures based on it have a large free volume within the polymer matrix. The polymer is potentially applicable for the separation or enrichment of gas, vapor or liquid mixtures. The use of the polymer, based on the high free volume, is especially suitable for separating the gas as a membrane material. Fritsch and collaborators (J. Mem. Sci. 251, 263-269 (2005)) obtain relatively high permeabilities.

In addition to gas separation, PIM-based membranes are also potentially applicable for the separation of chiral molecules, such as amino acids, for the separation of organics, for example, alcohol from aqueous systems, for isomeric separation, in pharmacy and biotechnology15 for the separation of proteins or other thermally unstable components, in fermenters and bioreactors for gasification and biomass separation, as well as for the removal of microorganisms from air and water.

Other potential application possibilities are water purification, the detection or removal of oligocomponents or metal salts from air or water, the separation of liquid mixtures with pervaporation (for example, in the production of ethanol), as well as the separation of gas / steam (for example, separation of organic vapors from gas) and the liquid-liquid separation of organic components or also the improvement of the yield in equilibrium reactions through selective removal of the product. The separation of dissolved solids, such as, for example, homogeneous catalysts, is not described. The membrane thicknesses indicated from 10 to 500 pm are also too thick for the desired separation task.

WO 2005/113121 A1 describes the production of membranes composed of a thin layer of a microporous material with high intrinsic myoporosity. In addition to the production of membranes, possible applications of membranes are also mentioned, such as fluid separation and the separation of low molecular weight solids from fluids. The separation of hydrogen and hydrocarbons, N ₂ or CO, the separation of CO ₂ , H ₂ O and H ₂ S from natural gas, the separation of nitrogen and oxygen, the separation of VOCs (compounds organic volatiles) and other lower hydrocarbons from air and other gases, the separation of traces of organic components from aqueous flows, as well as the separation of low molecular weight components and oligomers from fluids and especially solvents.

The disadvantage of such processes known in the prior art is that the processes either do not sufficiently protect the catalytic system and, with this, can separate it supporting the activity and / or the active catalytic systems cannot be sufficiently retained. Especially in the retention of an active catalytic system of less than 1500 g / mol, which has an essentially lower molar mass than the catalyst species grouped, it is difficult to separate the components with a membrane from each other. a molar mass difference of a few 100 g / mol. At the same time, the membrane for the organic components has to be permeable enough to allow an economical process.

Since for the protective enrichment of a catalytic system of hydroformylation process flows of upper olefins (C4 and higher), which consists of the metal complex catalyst and its groups, as well as the free ligand, no satisfactory solution is known, object was to develop a process that separates the process flow containing the catalytic system (for example, reactor discharge or bottom product) into an enriched flow in the catalytic system and in an exhausted flow from the catalytic system and has a high degree of retention for the catalytic system, especially for the metallic component.

The technical object of the invention, therefore, is to make a process available for the enrichment of a homogeneous catalyst, in which the catalytic system can be enriched or separated with the achievement of its activity, in which the process must present a high degree of retention for the catalytic system, no diluents are needed for the reco7 / 26 recovery and no clustering of the metal fraction of the catalyst or decomposition of the catalytic complex is also observed.

This technical object is solved by a process for the enrichment of a homogeneous catalyst from a process flow, which contains this homogeneous catalyst as a component, in which the process current is conducted through at least one membrane and in which the membranes consist entirely or partially of a polymer, which has planar polymeric units, which are connected with each other through a rigid linker, the linker being wound around itself, so that at least one planar polymeric unit is connected via the linker in a non-coplanar arrangement with at least a second planar polymeric unit.

These polymers are referred to below as polymers with intrinsic microporosity (PIM).

Surprisingly, it was found that both from an organic reaction discharge from a metal catalyzed reaction, as well as from a distillate sediment enriched with high boiling solvents, produced from the reaction discharge, which contains solvents with a high boiling point. boiling, metal complexes, their agglomerates as well as free binders, it is possible to separate high-boiling solvents, product and starting products from the catalytic system by means of one or more membrane (s), with the retention for the metal component by membrane is greater than 70% and for the free binder, greater than 60%, if the separation is carried out in membranes, which contain polymers with intrinsic microporosity (PIM).

Preferably, the process is carried out with a separation limit of 400 to 2000 g / mol in the temperature range of 40 to 150 ° C and in a range of transmembrane pressure (differential pressure on the membrane) from 500 to 6000 KPa (5 at 60 bar).

Also at concentrations of high boiling solvents above 50% by mass, no addition of a diluent is necessary, as also at high concentrations of high

8/26 boiling the permeate flow and the selectivity of the separation is high enough for a technical realization. It is surprising that with PIM-based membranes, the catalyst complexes, whose molar masses are in the same order of magnitude as that of high-boiling solvents, are better retained than high-boiling solvents.

High-boiling solvents in the sense of the invention, are substances whose boiling point is higher than that of primary hydroformylation products (aldehydes and / or alcohols with one carbon atom more than the olefin used) and which have molar masses higher and are formed during hydroformylation. These include aldolysation products and acetalisation products, as well as esters, which are formed through the reaction of alcohols and acids, in which alcohols and acids are formed by disproportionate aldehydes. High boiling point solvents that are present in hydroformylation process streams generally have boiling points above 55 ° C with 0.1 MPa.

In a preferred embodiment, the polymers have spirobisindane bonds within the polymeric structures, which act as linkers.

In a preferred embodiment, the polymers have substructures within the substituted or unsubstituted polymer structures of spirobisindane, which act as linkers.

Spirobisindan bonds in the sense of the invention, are 1,1'spirobis [indano], 1,2'-spirobis [indano] and 2,2'-spirobis [indano]; whose structures can be represented as follows:

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The spirobisindane bond is not a chemical bond in the strict sense, but rather, a substructure arranged between the polymers.

A particularly preferred spirobisindane bond is the 3,3,3 ', 3'-tetramethyl-1, Tspirobis [indane] substructure:

Polymers are particularly preferred as the active membrane material, which has repeated units of one or more of the following formulas, where n represents the number of units and is preferably between 10 and 100000.

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The above polymers are hereinafter referred to as PIM (polymers with intrinsic microporosity).

By enrichment in the sense of the invention, it is understood not only the enrichment of the homogeneous catalyst, but also, the complete separation of the homogeneous catalyst from the process stream.

It is advantageous that PIM-based membranes, in comparison with current membranes, have a particularly high retention of solids dissolved in organic solvents, such as homogeneous catalysts and their binders and, at the same time, have a high permeate flow.

In addition, it is possible to obtain a particularly careful separation for the catalytic system, if the catalytic system is processed as much as possible in the presence of carbon monoxide and hydrogen, because by this means, the grouping process can be additionally prevented. An overlap with carbon monoxide, as well as hydrogen, is especially possible when separating membranes.

The amount of synthesis gas during the separation should be superimposed at least on the stoichiometric quantity necessary for the formation of the active catalyst species, in order to prevent the formation of inactive or even irreversible catalyst species.

Membrane Connection

The process according to the invention can be carried out with the use of one, two or more membrane (s) or with the use of one, two or more stages of membrane separation. Depending on the membrane separation capacity and the desired retention, it is possible to achieve the desired retention by connecting several stages of membrane separation in series. In the process according to the invention,

11/26 specially carried out two or more stages of membrane separation. The membrane separation stages can be directly connected in series. The series connection can be carried out in such a way that either the retentate or the permeate, preferably the permeate from a first membrane separation stage is conducted as a supply current to another membrane separation stage. The membrane separation stages possibly subsequent to the first membrane separation stage according to the invention can also be carried out under conditions similar to the first. In a membrane separation stage, a membrane or several membranes can be used. In a membrane separation stage, preferably two or more membranes are used.

In a multi-stage separation process, it may be advantageous to use different membranes in the membrane separation stages. Thus, in a membrane separation stage pre-connected to a membrane separation stage, a more permeable membrane is preferably used. The classification that occurs in this case leads to a better permeability in the post-connected membrane separation stage.

In the process according to the invention, the upper temperature limit in the membrane separation stages is predetermined by the stability of the membranes used and the stability of the catalytic system. The lower temperature limit depends on the viscosity of the solution to be separated and on the temperature-dependent solubility of the catalytic system therein. In the process according to the invention, a membrane separation stage, especially the first membrane separation stage, is preferably carried out at a temperature of 40 ° C to 150 ° C, particularly preferably at a temperature of 60 ° C to 90 ° C. If in the process according to the invention, those used in the hydroformylation of C ₁₂ -olefins are used to separate catalyst from hydroformylation reaction mixtures, then the membrane stage, especially the first membrane stage, is preferably carried out at an

12/26 temperature from 60 ° C to 90 ° C. If in the process according to the invention, those used in the hydroformylation of C ₈ -olefins are used to separate the catalyst from the hydroformylation reaction mixtures, then the membrane stage, especially the first membrane stage, is preferably carried out at a temperature of 40 ° C to 80 ° C. The execution of the process according to the invention, at the preferred temperatures can cause, on the one hand, a greater flow through the membrane. On the other hand, maintaining the mentioned preferred temperature ranges, a decomposition of the catalyst is avoided which, in addition, can lead to losses of active catalyst and a deposition of decomposition products of the catalyst on the membrane. Through a deposition, the quantitative current through the membrane can be reduced. In the extreme case, the quantitative flow can be entirely overcome by the blockade.

The transmembrane pressure (pressure in the membrane between the retentate and permeate side), in which the process according to the invention, is preferably carried out, preferably amounts to 500 to 6000 KPa (5 to 60 bar), particularly preferably 1000 at 3000 KPa (10 to 30 bar).

In the process according to the invention, PIM membranes can be used which, based on their chemical or physical properties, are suitable for retaining metal complex catalysts, especially phosphorus-organic metal complex catalysts, to a degree of at least 60% , especially above 80% and have a separation limit of 400 to 2000 g / mol. Another condition for the usefulness of the membrane is that the membrane must be stable against all compounds present in the reaction mixture, especially against solvents. PIM

By the designation microporous, materials that could be designated as nanoporous are also understood. So far, there are two classes of intrinsic micropore materials. Zeolites and amorphous activated carbon. Due to the lack of solubility in organic solvents, it is not possible to produce any films and, therefore, any membranes from these materials. This is different in polymers.

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PIM (polymer with intrinsic microporosity) is a newly developed class of polymers, which is preferably distinguished by a rigid spirobisindane bond, which causes a twist within the polymeric structure. The random distribution of the spiro bond prevents the sealing of the polymer. The rigid torsion (of the planar polymer chains) in the spirobisindane bond leads to a high proportion of free, free volumes linked to each other. Microporosity is designated as intrinsic, since it occurs independently of the thermal pre-treatment and processing of the polymer.

An example of a polymer with intrinsic microporosity is called PIM-1. By PIM-1 is meant one of the first polymers synthesized in this class of polymers. The CA Index name is 1,4 benzenodicarbonitrila, polymer with 2,3,5,6-tetrafluoro- ^{2,2, 3,3,} tetrahydro-3,3,3 ', 3'tetrametil-1, T -spirobis [1H-indene] -5,5 ;, 6,6'-tetrol with the number CA 67645015 48-9. PIM-1 is obtained from the reaction of SS ^ .e-tetrahydroxy-SAS ^ S-tetramethyl1,1-spirobisindane with 2,3,5,6-tetrafluorphthalonitrile:

Other examples of polymers with intrinsic microporosity are shown in US2006 / 0246273A1 and in W02005 / 113121.

Other examples of comonomers that can be used to modify PIM-1 are:

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Comonomer 3, in this case, is produced through the bromination of spirobisindane.

Other examples of starting substances are 9,9'-spirobisfluorenes, modified as 2,2'-dicarbonoxy-9,9'-spirofluorenes or 2,2'-diamino-9,9'-spirobisfluorenes, which are suitable for production of intramically microporous polyamides and polyimides.

In addition to the polymers with intrinsic microporosity mentioned above, the membranes may contain other materials. The membranes may have specially supporting or supporting materials, on which the PIM is applied as a thin, active separating layer. In these composite membranes, in addition to the membrane itself, there is also a support material. EP 0.781.166 describes a selection of support materials, to which explicit reference is made. In addition, in the applicable membrane according to the invention, reinforcing materials, such as, for example, particles of inorganic oxides or inorganic fibers, such as, for example, ceramic or glass fibers, may be present which increase the stability of the membranes, especially against pressure variations or high pressure differences. The thickness of the membrane separation layer for the process according to the invention is preferably 10 - 1000 nm, particularly preferably 100 - 700 nm.

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Technical Modules

The membranes are used in the process according to the invention, preferably in the form of membrane modules. In these modules, the membranes are arranged in such a way that the retentate side of the membrane can be overflowed in such a way that the polarization of the concentration of the separate components, here the catalyst-ligand system, reacts against and, in addition, the force required drive (pressure) can be recorded. In the permeate collection chamber, the permeate is joined on the permeate side of the membrane and removed from the module. Conventional membrane modules feature membranes in the form of membrane discs, membrane pads or membrane bags. In the process according to the invention, membranes are preferably used in the form of membrane modules, which feature membrane modules with module systems in open channel pads, in which the membranes are thermally welded or glued to form bags or pads. wide-spacer folded membranes or modules, in which the membranes are glued or welded together to form membrane pockets or membrane pads and wrapped with feed-spacers around a permeate collecting tube.

Overflow, Separation Stage

To avoid depositions on the membrane, certain proportions of current must be maintained within the membrane stages. It has been shown that the danger of deposition of a current depends on its turbulence and, therefore, its Reynolds index. In this way, regardless of the type of construction of the membrane module, it must be observed, so that the Reynolds index is between 55 and 13500, preferably between 100 and 3500 and very particularly preferred, between 170 and 900. In this case, the kinematic viscosity should be less than 10 mPas and preferably 1 mPas. Deposition is avoided at these current rates.

For the conversion of these current proportions, when using coiled membranes with a tube length of 1 m and a loss of

16/26 pressure of 150 KPa (1.5 bar) and a kinematic viscosity of the medium of 1 mPas to avoid depositions on the membrane, the process is preferably carried out in such a way that the membrane separation stage, especially the first stage membrane separation speed is present with an overflow rate in the membrane of 0.1 to 15 m / seconds, preferably 0.2 to 4 m / seconds, preferably 0.3 to 1 m / second.

The process according to the invention is preferably operated in such a way that the solution to be separated is carried as an affluent to the membrane and the stream of the retentate is partially returned to the membrane, previously associated with the solution to be separated. The part of the retentate stream, which is not returned to the membrane, is either used as an adduction stream for one or more stages of separation or else is returned to the reaction.

If a stream with a small proportion of high boiling solvents and a high proportion of primary products is conducted to the membrane separation stage, as is the case in a reactor discharge without prior concentration of high boiling solvents, the proportion of the volumetric flow of the permeate flow to the feed flow of the reactor (without the retentate renewal), matters in 1 to 1.1 to 1 to 5, preferably from 1 to 1.4 to 1 to 3 and particularly preferably , from 1 to 1.6 to 1 to 2.

If in the opposite case, a clearly enriched stream of solvents with a high boiling point compared to the reactor discharge, is conducted to the membrane separation stage after the reactor, for example, by a thermal separation stage, then the flow ratio volume of the permeate flow to the reactor feed flow (without retentate renewal), preferably 1 to 5 to 1 to 20, preferably 1 to 7.5 to 1 to 12.5 and 1 to 9 to 1 to 11.

It can be advantageous if the volumetric flow, which is conducted through the membrane, is clearly greater than the volumetric flow of the flow

17/26 of the permeate, since, in this simple way, a high overflow rate in the membrane can be adjusted. Preferably, the ratio of the volumetric flow of the flow conducted to the membrane, especially the first membrane of the first membrane separation stage (inflow of the reactor including retained retentate) to the permeate flow from 10 to 10,000 to 1, preferably from 50 to 5000 to 1 and particularly preferably, from 200 to 2000 to 1. Therefore, preferably a relatively high volumetric flow is conducted in a circle through the membrane. The size of the portion of the retentate flow, which is returned to the reaction or to another separation, results from the difference in the feed flow (without retentate retentate) and permeate flow.

In the case of higher permeabilities, it can also be advantageous to connect the membranes in a pine structure.

As a feed flow for the separation of the membrane, the reaction discharge of a reaction catalyzed by organic metal complexes can be used directly or a concentrate produced therefrom. The reaction discharges contain starting products, primary products, by-products, such as, for example, high boiling solvents, the catalytic system and possibly a solvent. If this mixture is processed according to the invention, the catalytic system, especially the metal complex, predominates in the retentate. With the permeate, which is processed and another stage of separation, the starting products, products and high-boiling solvents are separated together. In this case, the flow of the permeate is essentially greater than the flow of the retentate, which is not returned to the membrane. This results in a large membrane area and non-optimized retention of the catalytic system.

Therefore, preferably, most of the starting products and products are previously separated through a thermal separation stage. Such a thermal separation stage can be carried out, for example, by one or more thermal separation devices, such as, for example, thin layer evaporators, downward film evaporators, flash evaporators or distillation columns. As a top product,

18/26 in that case, essentially starting products and primary products are separated. As a base product, a mixture is obtained with high boiling solvents and the catalytic system. If the reaction mixture is a hydroformylation mixture, the top product generally contains the hydroformylation product, such as, for example, aldehyde and / or alcohol, as well as possibly unreacted hydrocarbons, such as, for example, olefins or compounds aliphatics and eventually solvent used in hydroformylation, which has a boiling temperature in the range of hydroformylation products or lower, which can be carried out for further processing. As a background product of the thermal separation stage, a mixture is obtained, which contains the complex catalyst and / or free binders, possibly a solvent with a boiling point greater than the hydroformylation product, as well as high-point solvents. boiling point formed during hydroformylation.

The proportion of high-boiling solvents in the bottom product is, depending on the reaction conditions and product used, between 50 and 98% by mass, especially between 60 and 90% by mass. These solutions can be carried out to separate the membranes without adding a diluent.

Optionally, before the thermal separation stage, the reaction mixture can be separated by means of a membrane in a flow with a higher concentration of catalyst and in a flow with a lower concentration of catalyst. The flow with the highest concentration of catalyst is returned to the reactor. The flow with the lowest catalyst concentration is conducted to the thermal separation stage. Such a process is described, for example, in DE 10 2005 046250.2.

With the aid of the present invention, it is possible to separate mixtures, which are formed in reactions with the use of homogeneously dissolved metal catalysts.

Examples of such reactions are hydrogenations, hydroformylations, metatheses, hydrocyanisations and hydrocarboxalkylations of olefins. Preference is given to hydroformylation mixtures, which

19/26 contain rhodium complex catalysts.

Hydroformylation reaction mixtures can originate from processes for hydroformylating olefins, preferably with 2 to 25 carbon atoms, particularly preferably 4 to 16, most particularly preferably, from 6 to 12 and especially from 8 , 9, 10, 11 or 12 carbon atoms, in the corresponding aldehydes. Most preferably, the hydroformylation reaction mixture has an aldehyde as a hydroformylation product, which is selected from aldehydes having 5 to 17 carbon atoms, preferably 9 or 13 carbon atoms, especially isononanal and isotridecanal.

The complex catalysts present in the hydroformylation reaction mixture and / or the free organophosphate ligands can be the compounds and complexes known in the art. Preferably, the complex catalysts or free linkers have such linkers, which are selected from phosphines, phosphites, phosphites, phosphonites. In that case, the linkers may have one or more phosphine, phosphite, phosphonite or phosphite groups. Likewise, it is possible that the ligands have two or more different groups selected from the phosphine, phosphite, phosphonite or phosphite groups. The ligands can be especially bisphosphites, bisphosphines, bisphosphonites, bisphosfinites, phosphonophosphites, phosphonophosphonites, phosphonophosphites, phosphophosphonites, phosphophosphites or phosphonophytosphites. The complex catalyst linkers and the free linkers can be the same or different. Preferably, the phosphorus-organic linkers of the complex catalyst and the free linkers are the same.

Examples of employable complex catalysts or binders and their production and use in hydroformylation can be found, for example, in EP 0.213.639, EP 0.214.622, EP 0.155.508, EP 0.781.166, EP 1,209,164, EP 1,201,675, DE 10,114,868, DE 10,140,083, DE 10,140,086, DE 10,210,918 or WO 2003/078444, to which explicit reference is made.

Examples of preferred binders are:

phosphines: triphenylphosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine, tris (o-tolyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (p-dimethylaminophenyl) phosphine, tricyclohexylphosphine,

20/26 tricyclopentylphosphine, triethylphosphine, tri- (1-naphthyl) phosphine, tribenzylphosphine, tri-n-butylphosphine, tri-t-butylphosphine.

Phosphites: trimethylphosphite, triethylphosphite, tri-n-propylphosphite, tri-i-propylphosphite, tri-nbutylphosphite, tri-i-butylphosphite, tri-t-butylphosphite, tris (2-ethyl-hexyl) phosphite, triphenyl 4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methoxyphenyl) phosphite, tris (2-t-butyl-4methylphenyl) phosphite, tris (p-cresyl) phosphite.

Phosphonites: methyldiethoxyphosphine, phenyldimethoxyphosphine, phenyldiphenoxyphosphine, 2-phenoxy-2H-dibenz [c, e] [1,2] oxaphosphorine and its derivatives, in which the hydrogen atoms are entirely or partially replaced by alkyl and / or aryl radicals or atoms halogen.

Common phosphinite binders are diphenyl (phenoxy) phosphine and its diphenyl (methoxy) phosphine and diphenyl (ethoxy) phosphine derivatives.

In addition, hydroformylation mixtures may have a linker that has an acyl- or heteroacylphosphite or an acyl- or heteroacylphosphite group as organophosphate linkers. Ligands that have acylphosphites or acylphosphite groups, their production and their use in hydroformylation are described, for example, in DE 100 53 272. Ligands that present heteroacylphosphites and heteroacylphosphite groups, their production and their use in hydroformylation are described, for example, in DE 10 2004 013 514.

In the following, the process according to the invention is described by means of examples, without the invention, whose protection area resulting from the claims and the specification, is restricted to them.

The process according to the invention, for the separation of higher boiling point components from homogeneous catalysts or homogeneous catalytic systems, through separation with membranes based on a polymer with intrinsic microporosity (PIM) is described below by means of examples for the hydroformylation of C4 to C ₆ olefins with rhodium complex catalyzed.

According to figure 1, the starting products (1) of hydroformylation, olefin and synthesis gas are conducted to the reactor (R). In the presence of the catalytic system exposed in the reactor, hydroformylation is carried out

21/26 of the olefin to aldehyde. The reacted starting product, such as aldehyde and by-products and by-products, among them, high-boiling solvents, such as aldol condensation products and unreacted starting product, as well as the catalytic system, are removed from the reactor as reaction mixture (2) and conducted to a selective membrane separation stage (M). In that case, an enrichment is carried out on the retentate side (3) and a depletion of the catalyst or catalytic system on the permeate side (4).

Figure 2 shows an enlargement of the process of figure 1, in which the permeate (4) of the membrane separation stage is conducted to a thermal separation stage (D). In the thermal separation stage, the permeate flow (4) is separated into a flow (6) enriched with higher boiling point components, such as by-products of the reaction fraction, as well as catalyst components not retained in the membrane separation and a lower boiling point product flow (5), containing predominantly aldehyde. In order to avoid enrichment of higher boiling point by-products in the process, the flow (6) or a partial flow (8) of the flow (6) can be discharged from the process. Unless it is necessary to discharge the entire flow (6), it may be advantageous to redirect the flow (7) predominant to the reaction, especially if the flow (7) still contains fractions of the catalytic system.

Depending on the impairment of the flow (6) of catalyst components, it may be advantageous to separate flow 6, through a second membrane separation stage, into a flow (7) enriched with catalyst and a flow (8) depleted so corresponding with catalyst, for the ejection of components with high boiling point (see figure 3). Depending on the activity of the catalyst enriched in the current (7), it may be advantageous to direct this flow directly or indirectly to the reaction.

The connection according to figure 3, can also be advantageous without the membrane separation stage after discharge of the reaction.

Figure 4 shows such a connection.

Another object of the invention is a process for the production of tri22 / 26 decanal, which comprises the following stages:

The. hydroformylation of tributene to tridechannel using a homogeneous catalytic system, consisting of rhodium and an organophosphate compound,

B. distillation separation of the reaction discharge in a distillate, which does not contain reacted olefins and aldehydes and a bottom product contains the high boiling solvent and the catalytic system,

ç. carrying out the process according to the invention, for the enrichment of a homogeneous catalyst, in which the high-boiling solvents are separated from each other as permeate and the catalytic system, as retentate,

d. retentate renewal with the enriched catalytic system in the hydroformylation reactor.

In a preferred embodiment, a tributene is used for the production of the tridechannel, which is produced by the oligomerization of linear butenes in solid nickel-containing catalysts.

In a particularly preferred embodiment, the organophosphate compound is tris (2,4-dithercbutylphenyl) phosphite.

Also without any further implementation, it is assumed that someone skilled in the art can use the report described above to the fullest extent. Therefore, the preferred embodiments and examples should be considered merely as a descriptive publication and not in any way be interpreted as a limitation. In the following, the present invention is illustrated in detail based on examples. Alternative embodiments of the present invention can be obtained in a similar manner.

Examples

Example according to the Invention

As an example, the challenging separation task was selected according to figure 4 of the previous connections for the membrane separation stage, based on the high fraction of high boiling solvents. In the case of the reaction, it is a hydroformylation of a

23/26 mixture of dodecene (tri-n-butene) catalyzed with rhodium / phosphite. The rhodium precursor used is rhodium acetylacetonatodicarbonyl and the ligand used is tris (2,4-di-tert-butyl-phenyl) phosphite. The rhodium concentration imported in 10 mg / kg. The rhodium for the binder proportion imported in 20. The reacted starting product, such as the aldehyde (isotridecanal) and by-products and secondary products, among them, the high boiling solvents such as the aldol and product condensation products unreacted starting point, as well as the catalytic system, are conducted to a thermal separation stage, whose bottom enriched with high boiling solvent and catalyst, is conducted to the membrane separation stage. The fraction of high-boiling solvents is above 50%. The molar mass difference between the species of active catalysts and the high boiling solvents is less than 500 g / mol.

It was possible to show, for example, that the retention of rhodium with a PIM membrane in the flow of high boiling solvents is greater than 95% (figure 5). The membrane filtration was carried out, in this case, for example, with a transmembrane pressure of 2500 KPa (25 bar) and with a temperature of 60 ° C. The overflow on the supply side imported at 1.7 m / s, the loss of tube pressure was less than 100 KPa (1 bar), the Reynolds index imported at around 1200. This high retention could be proven for a duration of test over 20 days. The permeate fluxes obtained in this case are between 0.63 and 1.41 kg / (m ² h). The rhodium concentrations in the membrane separation stage feed are 50 to 133 mg / kg.

Comparative Example

Tests have shown that the DE 10 2005 060784A1 process procedure cannot be applied for the separation task according to the process. The essential reason is the insufficient selectivity of the membranes and the membrane materials mentioned therein.

Table 1 shows the corresponding results for the selection of membrane types mentioned in DE 10 2005 060784A1. In the case of feeding the membrane separation stage, it is treated, as in the case of

24/26 example according to the process, of a discharge flow from the reactor enriched with high boiling solvents of rod / phosphite catalyzed dodecene hydroformylation. This flow corresponds correspondingly to the reacted starting product, such as the aldehyde (isotridecanal) and subproducts and secondary products, among them, high boiling solvents, such as aldol condensation products and unreacted starting product, as well as the catalytic system. The ceramic membranes of Inopor® and Velterop® have a good permeate flow, but they are not able to retain the catalytic system by far. Polymeric membranes have an increased retention compared to ceramic membranes, however, not enough for the catalyst. In addition, the Starmem 240® polyimide membrane has an inadequate low permeability.

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Table 1 TMP = transmembrane pressure

temperature [° C] CM 150 06 09 TMP (KPa) [bar] 2000 [20] 1500 [15] 3000 [30] 2500 [25] CM AND * _ç O X 3.08 11.42 0.29 1.74 retention [%] 45.0 19.5 05 Μ ^- permeate Rh [mg / kg] 62 62.5 27.5 food Rh [mg / kg] I 20 77 120 120 material CM O i— O O CM < 0. PDMS manufacturer/ membrane Inopor nano 0.9 nm Velterop 0.1 nm MET Starmem 240 GMT oNF2

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The examples show that with the process according to the invention, compared with the state of the art processes, considerably better enrichment of the catalytic system is possible. Thus, the process, based on the higher degree of retention for the catalytic system, can be carried out in a considerably more economical way. This is especially true of catalytic systems, which contain valuable metals, such as rhodium.

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Claims (18)

1. Process for enriching a homogeneous catalyst in a process flow, which contains this homogeneous catalyst, as a component, the process flow being conducted through 5 at least one membrane and in which the membrane consists entirely or partially of a polymer, which has planar polymer units, which are connected with each other through a rigid linker, the linker being twisted in itself, so that at least at least one planar polymeric unit is connected in a non-clamping arrangement10 with at least one second planar polymeric unit, where within the polymeric structure, where the polymer has in its internal structure spirobisindane bonds acting as ligands, characterized by the fact that the process flow contains high-boiling solvents and homogeneous catalyst from an organic reaction discharge15 homogeneously catalyzed through a reaction catalyzed by organic metal complexes and the high-boiling solvent is separated with the permeate and the catalytic system remains in retentate, where the process flow is a reaction of product production, with distillate sediment and enriched with high point solvents 20 boiling. 2. Process according to claim 1, characterized by the fact that the polymer has repeated units of one or more of the following formulas, where n is the number of units and is preferably in the range of 10 to 100000 Petition 870170090094, of 11/22/2017, p. 4/10 2/4 3. Process according to claim 2, characterized by the fact that the homogeneous catalyst contains one or more metal complexes. Process according to any one of claims 1 to 3, characterized by the fact that the process is carried out on membranes with a separation limit of 200 to 2000 g / mol. 5. Process according to any one of claims 1 to 4, characterized by the fact that the process is carried out at a temperature of 40 to 150 Ό. 10 Process according to any one of claims 1 to 5, characterized by the fact that the process is carried out at a transmembrane pressure of 0.5 to 6 MPa. 7. Process according to any one of claims 1 to 6, characterized by the fact that the process is carried out in the presence of 15 carbon monoxide and / or hydrogen. 8. Process according to any one of claims 1 to 7, characterized by the fact that the process is carried out using 1 to 3 membranes. 9. Process according to any one of claims 1 to 20, characterized by the fact that the process is carried out using Petition 870170090094, of 11/22/2017, p. 5/10 3/4 of 1 to 3 stages of membrane separation. 10. Process according to any of claims 1 to 9, characterized by the fact that the fraction of the high boiling solvents in the process flow is 50% to 98% by weight. 5 Process according to any one of claims 1 to 10, characterized in that the process is carried out without adding a diluent. Process according to any one of claims 1 to 11, characterized by the fact that homogeneous catalysts of 10 metal complexes, which have at least one metal of 4 ° 5 ° 6 ° 7 ° 8 ° 9 ° or 10 ° group of the periodic table of the elements and at least one organic binder, are separated from high boiling solvents. 13. Process according to claim 12, characterized by the fact that metal complex catalysts containing organophosphate compounds are separated from high boiling solvents. Process according to claim 13, characterized by the fact that catalysts of metal complexes containing rhodium and organophosphate compounds are separated from high boiling solvents. 20 15. Process according to claim 14, characterized by the fact that the high-boiling solvents are separated from a process flow of a hydroformylation mixture, wherein the hydroformylation mixture has high-boiling solvents, at least one complex catalyst, which contains rhodium and a phosphorous organo25 compound and organophosphorus compounds. 16. Process according to any one of claims 1 to 15, characterized in that the thickness of the membrane separation layer is 10 to 1000 nm. 17. Process for the production of tridecanol, characterized by the fact that it comprises the following steps: (a) hydroformyl tributene to tridechannel using a homogeneous catalytic system, consisting of rhodium and an organophosphate compound, Petition 870170090094, of 11/22/2017, p. 6/10 4/4 (b) distill the reaction discharge in a distillate, which does not contain reacted olefins and aldehydes and a residual product containing the high boiling solvent and the catalytic system, (c) carry out the process, as defined in any one of claims 1 to 16, for the enrichment of a homogeneous catalyst, in which the high-boiling solvents are separated from each other as permeate and the catalytic system, as retentate, (d) renew the retentate with the enriched catalytic system for hydroformylation reactor. 18. Process according to claim 17, characterized by the fact that tris (1,4-dithercbutylphenyl) phosphite is used as an organophosphate compound. Petition 870170090094, of 11/22/2017, p. 7/10 1/3 2/3